ACS Organic & Inorganic Au最新文献_第3页

High-Yield Room-Temperature Aryl 211At Radiolabeling via Redox-Activated Column-Shipped 211At 利用氧化还原活化柱载2111at进行室温芳基2111at的高产量放射性标记

IF 5.2

ACS Organic & Inorganic Au Pub Date : 2026-08-05 Epub Date: 2026-06-15 DOI: 10.1021/acsorginorgau.6c00015

Jehan S. Perera, Jennifer M. Pyles, Adrianna L. Orsi, Christine C. Lawrence, Marcus Le, Gabriel C. Tabacaru, Lauren A. McIntosh, Sherry J. Yennello, Jonathan D. Burns

{"title":"High-Yield Room-Temperature Aryl 211At Radiolabeling via Redox-Activated Column-Shipped 211At","authors":"Jehan S. Perera, Jennifer M. Pyles, Adrianna L. Orsi, Christine C. Lawrence, Marcus Le, Gabriel C. Tabacaru, Lauren A. McIntosh, Sherry J. Yennello, Jonathan D. Burns","doi":"10.1021/acsorginorgau.6c00015","DOIUrl":"https://doi.org/10.1021/acsorginorgau.6c00015","url":null,"abstract":"Efficient late-stageformation of aryl–211Atbonds is relevant to expanding the scope of targeted α-therapyradiopharmaceuticals. In this work, a catalyst-enabled astatodeboronationapproach is evaluated using wet chemically regenerated 211At recovered from shipped 3-octanone-impregnated columns. A seriesof aryl boronic esters bearing electron-donating and electron-withdrawingsubstituents were radiolabeled under mild conditions, with reactionparameters examined through time-dependent studies. Radiochemicalconversions ranging from 68–97% were observed across the substrateset. Density functional theory calculations were employed as a qualitativeframework to contextualize relative B–C and At–C bondingdescriptors. Overall, this study demonstrates that wet chemicallyregenerated 211At can be applied to the late-stage labelingof aryl boronic esters under mild conditions and provides guidancefor future exploration of 211At radiolabeling strategies.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 4","pages":"414–421"},"PeriodicalIF":5.2,"publicationDate":"2026-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148693790","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Pursuing the Red-Shift in Glycoporphyrins─A New Synthetic Approach toward Glycoconjugates from the meso-Tetraethynylporphyrin Scaffold 追求糖卟啉的红移─中-四乙基卟啉支架合成糖缀合物的新方法

IF 5.2

ACS Organic & Inorganic Au Pub Date : 2026-08-05 Epub Date: 2026-06-25 DOI: 10.1021/acsorginorgau.6c00033

Jakub Mitrzak, Maciej Malinowski

引用次数: 0

An Axially Chiral Pyridyno-allenophane in a 2:1 Edge-to-Face Silver(I) Sandwich Complex: Synthesis and Structural Characterization 一种在2:1边对面银(I)夹心配合物中的轴手性吡啶-烯绿素：合成和结构表征

IF 5.2

ACS Organic & Inorganic Au Pub Date : 2026-08-05 Epub Date: 2026-06-22 DOI: 10.1021/acsorginorgau.6c00012

Jonathan Álvarez-García, María Magdalena Cid

引用次数: 0

Diastereoselective Synthesis of α-Fluoro-γ-lactams via Difluorocarbene-Triggered Cyclization and Rearrangement 二氟化烃引发环化重排法非对映选择性合成α-氟-γ-内酰胺

IF 5.2

ACS Organic & Inorganic Au Pub Date : 2026-08-05 Epub Date: 2026-05-14 DOI: 10.1021/acsorginorgau.6c00028

Maryam Jabbarpoor, Yanmei Li, Alex Akhundov, Jesse LeBlanc, Pier Alexandre Champagne, Christine M. Le

{"title":"Diastereoselective Synthesis of α-Fluoro-γ-lactams via Difluorocarbene-Triggered Cyclization and Rearrangement","authors":"Maryam Jabbarpoor, Yanmei Li, Alex Akhundov, Jesse LeBlanc, Pier Alexandre Champagne, Christine M. Le","doi":"10.1021/acsorginorgau.6c00028","DOIUrl":"https://doi.org/10.1021/acsorginorgau.6c00028","url":null,"abstract":"We report a difluorocarbene-enabled, diastereoselectivesynthesisof α-fluoro-γ-lactams from readily accessible β-aminoketonesand inexpensive, commercially available ethyl bromodifluoroacetate(EBDFA). Compared to established routes to this medicinally relevantmotif, our strategy avoids the use of costly electrophilic fluorinatingor deoxyfluorinating reagents, highlighting difluorocarbene as a versatileC1 and F building block. Density functional theory (DFT) calculationsreveal that cyclization is the stereodetermining step, with observeddiastereomeric ratios governed by Curtin–Hammett kinetics.In addition to activating EBDFA, the K2CO3 baseenables the favorable formation of a transient hemiaminal epoxideintermediate, with subsequent C–F bond formation proceedingthrough a nucleophilic fluoride ring-opening pathway. Overall, thiswork not only delivers a direct and modular route to stereodefinedα-fluoro-γ-lactams but more broadly expands our mechanisticunderstanding of difluorocarbene-mediated amine-carbonyl couplingreactions.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 4","pages":"430–437"},"PeriodicalIF":5.2,"publicationDate":"2026-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148693748","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Strategies for Enantioselective, Cascade, Valorizing, and Expanded Heterocyclic Piancatelli Rearrangements 对映选择性、级联、增值和扩展杂环Piancatelli重排的策略

IF 5.2

ACS Organic & Inorganic Au Pub Date : 2026-08-05 Epub Date: 2026-07-25 DOI: 10.1021/acsorginorgau.6c00050

A. Talim G. K, Michael Kizirian, Elias Picazo

{"title":"Strategies for Enantioselective, Cascade, Valorizing, and Expanded Heterocyclic Piancatelli Rearrangements","authors":"A. Talim G. K, Michael Kizirian, Elias Picazo","doi":"10.1021/acsorginorgau.6c00050","DOIUrl":"https://doi.org/10.1021/acsorginorgau.6c00050","url":null,"abstract":"The Piancatelli rearrangement of 2-furylcarbinols hasbecome aversatile platform for the rapid assembly of densely functionalizedcyclopentenones from renewable furan feedstocks. This Perspectivehighlights recent advances in four key directions: enantioselectivecatalysis, cascade processes for polycyclic scaffolds, biomass valorization,and expanded heterocyclic variants. Chiral Brønsted acid catalysis,frequently paired with photoredox or transition-metal cocatalysis,now delivers highly enantio- and diastereoselective aza- and oxa-Piancatellirearrangements, including three-component radical-mediated couplingsthat install diverse functionality in a single step. Strategic mergerof the rearrangement with downstream Diels–Alder, hydroamination,or Friedel–Crafts reactions provides efficient access to complexpolycyclic frameworks bearing multiple contiguous stereocenters. Parallelefforts have transformed 5-hydroxymethylfurfural (HMF) and 5-azidomethylfurfural(AMF) derivatives into bioactive cyclopentenones under sustainableand scalable conditions. Finally, the first interrupted aza-Piancatellirearrangement on pyrrole substrates has extended the transformationbeyond furans, enabling new amino Stenhouse photoswitches. These developmentsunderscore the enduring synthetic power of the Piancatelli rearrangementand point to exciting opportunities in asymmetric complex-moleculesynthesis, functional molecular materials, and expanded heterocyclicreaction development.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 4","pages":"361–385"},"PeriodicalIF":5.2,"publicationDate":"2026-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148693712","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Catalytic Amidation of Carboxylic Acids Using ortho-Aminophenylboronic Acids 邻氨基苯基硼酸催化羧酸酰胺化。

IF 5.2

ACS Organic & Inorganic Au Pub Date : 2026-08-05 Epub Date: 2026-05-12 DOI: 10.1021/acsorginorgau.6c00021

Veera K. Bruce-Salmenkivi, Mikko Passiniemi, Petri M. Pihko

引用次数: 0

Regioisomeric Control of Chemiexcitation Efficiency in Lophine Silylperoxides through Reaction-Path Topology and Excited-State Accessibility 基于反应路径拓扑和激发态可及性的有机硅过氧化物化学激发效率的区域异构体控制

IF 5.2

ACS Organic & Inorganic Au Pub Date : 2026-08-05 Epub Date: 2026-06-29 DOI: 10.1021/acsorginorgau.6c00037

Diego Ulysses Melo, Andreia Boaro, Roberta Albino dos Reis, Leonardo Martins Carneiro, Paula Homem-de-Mello, Fernando Heering Bartoloni

{"title":"Regioisomeric Control of Chemiexcitation Efficiency in Lophine Silylperoxides through Reaction-Path Topology and Excited-State Accessibility","authors":"Diego Ulysses Melo, Andreia Boaro, Roberta Albino dos Reis, Leonardo Martins Carneiro, Paula Homem-de-Mello, Fernando Heering Bartoloni","doi":"10.1021/acsorginorgau.6c00037","DOIUrl":"https://doi.org/10.1021/acsorginorgau.6c00037","url":null,"abstract":"This study investigates the chemiluminescence (CL) ofsilylperoxidesderived from lophines and their associated high-energy intermediates(HEIs), specifically 1,2-dioxetanes. Three regioisomeric silylperoxides(D1–3), differing in the positionof the –O– group, were synthesized, and theirCL and kinetic behavior under fluoride-induced decomposition wereexamined. Notably, the ortho-substituted derivative(D1) exhibits a 100-fold and 10-fold increase in singletexcited-state formation quantum yield compared to its meta (D2) and para (D3) counterparts,respectively. Computational analysis using density functional theory(DFT) and time-dependent DFT (TD-DFT) indicates that chemiexcitationproceeds through a single-step asynchronous-concerted mechanism withpronounced biradical character along O–O bond cleavage. Thedifferences in singlet quantum yields are rationalized by a combinedeffect of the extent of the biradical/near-degenerate region and therelative accessibility of excited-state surfaces along the reactionpath. In particular, the enhanced efficiency of D1 arisesfrom its prolonged residence in near-degenerate regions together witha more favorable energetic balance for singlet-state formation relativeto triplet-state stabilization. These findings provide a mechanisticframework for understanding substituent effects in chemiexcitationand suggest that tuning reaction-path topology and excited-state energeticsmay guide the rational design of improved chemiluminescent systems.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 4","pages":"460–473"},"PeriodicalIF":5.2,"publicationDate":"2026-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148693794","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

α-Fluoronitroalkenes as Fluorinated Building Blocks: Solvent-Controlled Functionalization with Hydrazones 作为氟化构件的α -氟硝基烯烃：与腙的溶剂控制功能化。

IF 5.2

ACS Organic & Inorganic Au Pub Date : 2026-08-05 Epub Date: 2026-07-06 DOI: 10.1021/acsorginorgau.6c00032

Matthew A. Saucier, Hamdan Alrefaei, Peggy A. McCluggage, Mohammed K. Abd El-Gaber, Tzu-Yu Huang, Sampad Jana, Sudeshna Roy

{"title":"α-Fluoronitroalkenes as Fluorinated Building Blocks: Solvent-Controlled Functionalization with Hydrazones","authors":"Matthew A. Saucier, Hamdan Alrefaei, Peggy A. McCluggage, Mohammed K. Abd El-Gaber, Tzu-Yu Huang, Sampad Jana, Sudeshna Roy","doi":"10.1021/acsorginorgau.6c00032","DOIUrl":"10.1021/acsorginorgau.6c00032","url":null,"abstract":"While α-fluoronitroalkenes havebeen widelyexplored in annulation and cycloaddition chemistry, controlled intermolecularC–N bond formation through conjugate addition remains largelyundeveloped. Moreover, solvent-controlled divergence between conjugateaddition and cyclization from identical starting materials has notbeen systematically demonstrated for α-fluoronitroalkenes. Herein,we report a base-mediated 1,4-conjugate addition of hydrazones to α-fluoronitroalkenes under aprotic conditions, affording N-fluoroalkyl hydrazones. In contrast, protic acidic conditionsdivert reactivity toward 4-fluoropyrazole formation, highlightinga solvent-controlled divergence in reaction pathways. This one-potprotocol tolerates a wide range of aromatic, heteroaromatic, and aliphaticsubstrates, providing isolable N-fluoroalkyl hydrazonesin moderate to high yields. This study expands the synthetic utilityof both hydrazones and α-fluoronitroalkenesas building blocks of interest for applications in organic synthesisand medicinal chemistry.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 4","pages":"386–391"},"PeriodicalIF":5.2,"publicationDate":"2026-08-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148689944","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Is the Signal Worth the Noise? A Practical Guide to Charge-Tagging for ESI-MS Reaction Monitoring 信号值得噪音吗？ESI-MS反应监测电荷标记的实用指南。

IF 5.2

ACS Organic & Inorganic Au Pub Date : 2026-06-03 Epub Date: 2026-05-01 DOI: 10.1021/acsorginorgau.6c00020

Charles Killeen, Maxine A. Turner, J. Scott McIndoe

{"title":"Is the Signal Worth the Noise? A Practical Guide to Charge-Tagging for ESI-MS Reaction Monitoring","authors":"Charles Killeen, Maxine A. Turner, J. Scott McIndoe","doi":"10.1021/acsorginorgau.6c00020","DOIUrl":"10.1021/acsorginorgau.6c00020","url":null,"abstract":"Electrospray ionization mass spectrometry (ESI-MS) hasemergedas a uniquely powerful platform for real-time reaction monitoring.However, because ESI-MS inherently detects only charged species, theionization process can alter the electronic structure, coordinationenvironment, or speciation of neutral analytes, thereby complicatingmechanistic interpretation. This tutorial review provides a practicaland mechanistic guide to the charge-tagging strategy as a solutionto these challenges. The conceptual basis of charge-tagging is examined:by appending a permanent ionic group to a ligand or substrate, ionization-inducedchemical modification is minimized, allowing faithful tracking ofsolution-phase speciation during catalytic transformations. Key designprinciples are discussed, including the selection of weakly coordinatingcounterions, optimization of electrospray response, mitigation ofaggregation and contamination, and preservation of steric and electronicproperties relative to neutral analogues. Synthetic approaches toboth anionic (primarily sulfonate-based) and cationic (ammonium andphosphonium-based) charge tags are presented in detail with emphasison practical considerations such as salt metathesis, regioselectivityin arene sulfonation, nucleophilic substitution strategies, and avoidanceof undesired reactivity. Representative applications in palladium-and ruthenium-mediated transformations illustrate how charge-taggedprobes enable kinetic analysis, identification of transient intermediates,and mechanistic discrimination under realistic conditions. By integratingtheoretical background, synthetic methodology, and practical troubleshooting,this review aims to equip practitioners with the tools needed to design,prepare, and deploy charge-tagged compounds as simply and effectivelyas possible.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 3","pages":"258–269"},"PeriodicalIF":5.2,"publicationDate":"2026-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148200131","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

An Atypical Dinuclear Copper(II) 1,2,4-Triazolyl Complex as a Catalyst for Palladium-Free Csp-Csp Homocoupling of Phenylacetylene 非典型双核铜（II） 1,2,4-三唑基配合物催化苯乙炔无钯Csp-Csp均偶联。

IF 5.2

ACS Organic & Inorganic Au Pub Date : 2026-06-03 Epub Date: 2026-04-14 DOI: 10.1021/acsorginorgau.6c00013

Lorenzo Luciani, Nicola Sargentoni, Magda Monari, Rossana Galassi

{"title":"An Atypical Dinuclear Copper(II) 1,2,4-Triazolyl Complex as a Catalyst for Palladium-Free Csp-Csp Homocoupling of Phenylacetylene","authors":"Lorenzo Luciani, Nicola Sargentoni, Magda Monari, Rossana Galassi","doi":"10.1021/acsorginorgau.6c00013","DOIUrl":"10.1021/acsorginorgau.6c00013","url":null,"abstract":"An unusual dinuclearcopper(II) complex, labeled as [L2Cu2(solv)2]•2(solv) (where solv = CH3CN or H2O and L = 3,5-bis(trifluoroacetamido)-1,2,4-triazo-1-yl),with L acting as an O,N,N′,O′-donor chelating ligand,was prepared by reaction with Cu2O. The single crystalXRD analysis and the susceptibility measurements revealed a pentacoordinateddinuclear Cu(II) complex with the two Cu atoms in a square pyramidalenvironment, doubly bridged by the 3,5-substituted triazolate ligandsand one coordinated acetonitrile in the apical position, completingthe coordination sphere. Systematic voids in the solid-state packingaccommodate two additional acetonitrile molecules; all of the acetonitrilemolecules can be readily replaced by water or other solvents. Thenew copper(II) complex was investigated as a catalyst in the Csp-Csp homocoupling reaction of phenylacetylene(Glaser-type reaction), yielding satisfactory results in terms ofboth isolated yields and procedural simplicity. For a better understandingof the catalytic results, spontaneous aggregation in solution ofthis copper(II) complex was investigated. The dilution experimentsin polar solvents, followed by UV–visible spectroscopy, highlightedthe self-aggregation behaviors, which were further corroborated byESI-MS analyses. The dissociative equilibrium constants, Kd, were determined in ethanol, Kd = 3.89 × 10–3 M, and in CH3CN, Kd = 8.10 × 10–2 M, evidencing the role of the solvent in the association process.","PeriodicalId":29797,"journal":{"name":"ACS Organic & Inorganic Au","volume":"6 3","pages":"270–276"},"PeriodicalIF":5.2,"publicationDate":"2026-06-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148200150","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0